Esters



"UNITED s'rATEs PATENT OFFICE Martin E. I JeL, assignor to I. I. (in Pont de Nemours & Company, Wilmington, Del a corporation oi Delaware Drawing. Application April 30, 1942,

Serial No. 441,223

'l claims. (or. 260-4103!) This invention relates to new synthetic dryin oils and to coating compositions containing them.

The higher grade natural drying oils, such as China-wood, perilla, and oiticica oils, are for the most part imported and are subject to wide fluctuation in price, quality, and availability. Some of these oils have a tendency to form films which "crystallize" or "frost." Previous attempts to provide synthetic substitutes having the desirable film-forming characteristics :01 these natural oils have been for the most part unsatisiactory in one or more ways. c

This invention accordingly has as its general objective the preparation of new esters which can be substituted tor the rapidly drying natural fatty .oilsin coating compositions into which fatty o s are ordinarily formulated.

Another objective is the preparation of new esters having film-forming properties, especially .drying rates, hardness, and toughness, of about the sameorder as, or better than, those of the natural drying oils. Y

,A. further objective is the proper combination of polyhydric alcohol and'monocarboxylic acids which will give esters, having such properties.

The'expression "a'cylacrylic acid" is used in a generic sense to designate any of those ketomonocarboxylic acids having an ethylenic double bond between the a and 5 carbon atoms and an .acyl group attached to either the a or ,5 carbon.

The novelproperties or the products of the invention are considered to depend from this parv ticular and peculiar arrangement of carboxyl group, ethylenic double bond, and ketone group. The remainder of the'molecuie is substantially immaterial provided the acid is monofunctionai," i. e.',*contains no groups, such as hyd'roxyl, primary amino, secondary amino, sulihydryl, and the like,

" which are known to react with the carboxyl group under normal esterificatlon ,conditions.

The simple esters referred to above can be prepared by reacting the polyhydric alcohol with the acylacrylic acid or appropriate esteriflable deriva tive thereof, such as an acid halide or an ester with a lower aliphatic moiEnydr'ic alcohol. The mixed esters can be-prepared in general by reacting the polyhydricalcohol, simultaneously orsuccessively, in either order, with the several mono- A still further objective is the preparation of waters from those monocarboxylic acids which have the particular types of unsaturation, and

other eiementsot chemical structure, which will impart rapid drying film properties to said esters. An additional objective is the provision of methods ofmaking these new esters.

Another objective is the preparation of new and improved coating compositions containingthese new esters.

The 'above'and other objects appearing hereinafter are accomplished by preparing, for example, by one of the methods subsequently described in detail, a polyhydric alcohol esteroi a monoiunctional acylacrylic acid. These esters may be simple esters (i. e., all the hydroiwls o! the poly-- hydric alcohol being esterifled'with one and the same acylacrylic acid) or they maybe mixed esters, in which the hydroxyis of the polyhydric alcohol are esterined with di ii'erent acylacrylic acids or with an acylacrylicacid and one or more other monoiunctional monocarboxylic acids'of s dii'l'erent structure. The latter acids are preferably unsaturated,- the acids of natural drying or semidrying oils being most useiul. The mixed esters can also be designated aspolyhydric alcohol mixed esters, the acyl radicals. oi which'comprise those of the acylacrylic acid and amouniunctionai monocarboxylic acid oi different strucure.

carboxylicacids or their vesteriiiable derivatives,

such acids including at least one acyiacrylic acid and, usually, at least one 'monoiunctional monocarboxyiic acid 01' different structure. It is to be noted, however, that the u-acylacrylic acids are in general relatively unstable as free acids, and their polyhydric alcohol esters, simple or mixed, are best prepared by ester interchange from an ester of the wacylacrylic acid with hydric alcohol.

In one of the preferred methods of carrying out the invention, the acylacrylic acid, or ester a volatile monothereoi with a volatile alcohol, is reacted with apolyhydric alcohol which has been partially esterified with a different monoiunctional monocarboxylicacid or acids. When these polyhydric alcohol partial esters are glycerol partial esters of a long chain fatty acid, they are most suitably obtained by heating fatty oils in the usual way with glycerol and, preferably, an ester interchange catalyst. In carrying'out this alcoholysis step, the oil and 'free poiyhydric alcohol, inproportions calculated to give the degree of alcoholysis desired, are placed, along with a small amount of alcoholysis catalyst (e. g., 0.01 to 0.1% litharge based on the oil), in a reactor fitted with. an

governed by compositions.

alone, or in blends with natural or synthetic ie ins and/or natural drying or semi-drying oils.

T, morefdetailed practice of the in 0., and the a ylacrylic acid, or esteriflable deriva- V tive, is introduced in approximately the amount sufiici'ent to esterit'y the free hydroxyl-groups calculated to be-present from the initial proportions oi oil and polyhydric alcohol.

' in an amount sui'iicient to produce boiling when a the temperature reaches about 200C. The distilling vapors of solvent and water of esterifica- .tion are passed through a downward condenser, the, water separated mechanically from the condensed liquids, and the solvent returned to thereaction vessel, the whole cycle or distillation.

separation of water, and return of solvent being 15 conducted in a continuous manner.

Dependin on the temperature of reaction, which in turn is the nature and amount of solvent employed, the reaction is usually completed within 4-15 hours; thus, when the temperature is around 200 C., the process is. usually completed within 4-10 hours. The "reaction can be accelerated if desiredby means of esteriflcation Icata-i lysts, such as sodium bisuliate'. The progress of the reaction can be followed by acid number de- 25 terminations, the heating being stopped when the acidnumber reaches or approachs .constancy, .or-at any-desired value. There is obtained a'viscous solution of the new drying oil from which the solvent can -beremoved, if de- I lowing the examples. l

sired, by'distillation or by forcing a rapid stream of carbon dioxide through the mixture. This oil can be formulated, by conventional methods used with natural drying oils, into valuable coatin For such purposes. it can he used Hot blending of these new oils with the naturaldrying ,or semi-drying oils gives coating composition vehiclesiof unique-properties.

illustrated in the following examples whereinthe amounts of the ingredients are by weight, such examples being given by way of illustrationand not as a limitation. ,Inthese examples, viscosi- 5' ties and colors are'given on the Gardner-Holdt A- hydrocarbon solvent, such as xylene or toluene, is next added mentioned, sufilcient of a 2% cobalt naphthenate solution has been used to give the indicated 'con-' lo lift of cobalt metal, this proportion being based The ester compositions in the title of each example do not mean that the product actually contains the stated percentages'of triglycerides, but are instead an index to the proportion of monocarboxylic acid radicals in the product. To illustrate, a product referred to i as having 24.4% -benzoylacrylic acid. glyceride and 75.6% linseed acids glyceride is a product prepared from proportions of reactants soflchosen as to yield theoretically a mixture of the two mentioned glycerides in the stated proportions by weight, 1. e., if it be assumed no mixed esteris' formed. Actually, such a product is considered to be composed principally of mixed glycerides, probably mixtures of mixed glycerides, though small amounts of simple gly'oerides, partial vglyceride's "(1, e., glycerol incompletely esterifled), free glycerol, and free the acylacrylic acid ester content is discussed fol- I Exsnrrtx l Glycerol mixed ester of linseed oil acids and p-benzoulacrylic acid Percent p-Benzoylacrylic acid glyceride 24.4 Linseed acids glyceride 75.6.

A partial glycerol ester of linseed oil acids, commother goo-d method bf preparing the monly called linseed oil diglyceride, is first prehydric alcohol mixed esters of this invention istoheat together a polyhydric alcohol, a polyhydric alcohol ester such as a drying or semi-( rvi oil, and sufficient acylacrylic acid or esteriflable derivative to react with the free hydroxyl groups present inv this mixture.

of stand points. The esterification reaction for the preparation of the dryin oil-is pref r b carried out at as low a temperature as is nractioal.' -Another-: such precaution is the ma nt V .nance of an inert atmosphereby the use of an "M 1 of carbon ide. is maintainedthroughoxygen-free inert gas. By complete or essential! of oxygen, superior colo isobtained, while, it the reaction is carried uts-t 3 high temperature in the presence'of oxyg n. poorer color, c'ombined'with decom osition d no complete 1 exclusion sometimes inferior drying, is encountered. To

under eactionf conditions. Thus. solvents e old samples of petroleum naphtha should not be used since the peroxides nsuallypresent inthese .rnaterials produce deleteriouseflecta- -.0ther oxygen-yielding compounds,- for example, oxidized drying oils,-should be excluded in order to. insure" 1 good color, and to avoid degradation'andlg ela .tion of the resulting compositions.

pared by heating 1300' parts .of alkali-refined linhours at 250 Chin an inert atmosphere; To 107 gram of this dislvceride are added 12 parts of toluene and 32 parts-oi ,s-benzoylacrylic acid-of melting point94-9'P- C. (obtainable from benzene v and maleic anhydride accordingto the general method outlined by von Pechmann, Ber. 15, 885

an (1882) and the solution is refluxed for 9.5 hours at 200-210" C. in an apparatus equipped to allow the condensation of toluene and water of eaterification, separation of the water, and return of toluene to the. reaction weasel. Aninert atmos- 'out' this esterification, andat the completion'of traces of unreacted acid. After being cooled and filtered, the resulting oil -;is found to possess'the following physical and analytical values: No

1.510;); hydroiyl' -No.zo.2,- acid No. 1.3. With' 0.03% cobalt, this oil dries" after 8 hours at room 7 ployed'shouldnot be those which contain or give ool e perature over wood and stel to. films which oil free oxygen or similar active products-during are-hard, light-colored, and tack-free; On bakthe reaction. For example. aged turpentine or I his, for; example at 100 C., drying is much faster,

and, if desired,'drlers can be eliminated. Dried films are-hard, glossy and-adherent,.andare sim 7o liar in many respects to those obtained from -(-Lhlm -avoqxloil-limedrosinvarnishes orfrom perilla oil-Amberolf' varnishes oi. about ill-gab 'lon oil len'gth." Unmodified linseed oil'under the same drying conditions is tacky and eventuallyntion. is 16 a-soft, weak film having residualt'ach hard.

over steel and undercoats after 8 months in Delaware show durability definitely superior to the above varnish controls.

The above product can be made intoavarnish as follows: 30 parts of theoil are bodied at 280 C. for 2.25 hours to a thin string. At this point, 7.6 parts of an Amberor resin and 0.14 part of lime are added with vigorous stirring. The re-.

sulting solution is heated for an additional 0.5 hour at 280 C., cooled to 150 0., and 38 parts of an aromatic hydrocarbon thinner added. After addition of lead naphthenate andmanganese resinate driers, the varnish is filtered. The viscosity oi the cooled varnish at 50% solids is-G-H.

Films of this varnish dry tack-free in 4 hours at room temperature and are light in color, clear, and after overnight dry are of a hardness similar to that of films from a perilla varnish of com,-

parable oil length. i

This oil can also be made into an enamel as follows: 50 parts of the oil, 25 parts 01 titanium dioxide, 25 parts of antimony oxide, and 20 parts 01' a hydrocarbon thinner are ground together to .give a dispersed system. Cobalt and lead driers in amounts of 0.03% and 0.3%, respectively, are added. This enamel dries in 10-15 hours at C. to films whicharetack free and I Exurru 2 Glycerol mixed ester of linseed oil acids and p- 2,4-dimethylbenzoul) acrylic acid p v Percent p-(ZA-dimethylbenzoyl) acrylic acid glyceride 27.0 Linseed acidsglycerideum 73.0

To 72 parts-0t thelinseed oil diglyceride described in Example 1 are added 25 parts oi 542,4-

dimethylbenzoyllacrylic acid of melting point 114 C. (prepared from xylene and maleic-anhydride by the general method ofHertzowna and I Maechelewski, C. Z, 34, II, 567) and '10 parts of toluene. ,.Ihis mixture is refluxed for 7 hours at 200-210 C. in the same type of apparatus described in the previous example. A vigorous stream of carbon dioxide is next blown through analytical values: hydroxyl No. 33.3; acid No.

3. 23; viscosity 24. Thin films cum oil containing 0.03% cobalt drier are dust-free in less than,3 hours at room temperature,and after 8-10 hours are hard and tack iree. Films oi this oil are similar to films oi the oil described in Example 1.

- Exsrlrn 3 Glycerol mixed ester of linseed oil acids and .p-henzoylacrylic acid I Percent; b-Benzoylacrylic acid g1yceride 20.0 Linseed acids glyceride 80.0

To 192 parts of alkali-refined linseed :oil are 'added' parts 01' p-benzoylacrylic acid inonohydrate (melting point 61 C.; neutraleq'uivalent 192), 7.1 parts of refined glycerol, and 15 parts of toluene. Aiterheating the mixture for 8.5 hours at 200 C., a homogeneous oil is obtained which,

after removal of solvent, is found to possess the following physical and analytical .values: Nu" 1.5020; hydroxyl No. 29.15; acid No.8.4'l;- visthe reaction mixture t 200 ,C. for 20minutes in order to remove so vent and unreacted acid. After being cooled and filtered, the resulting oil is found to possess the following physical and cosity V. Thin films ofthis oil containing 0.03% cobalt drier are dust-free in less than 4 hours and tack-free in about 8-10 hours at room temperature. Films of this oil are similar to films of the oil described in Example 1.

' Exlnnu: 4 V i Glycerol mixed ester of linseed 'oil acids and d-acetocrotonic acid 1 A Per cent d-Acetocrotonic acid glyceride 16.7 Linseed acids glyceride 83.3

To as parts-oi refined glycerol is added 30 parts of methyl c-acetocrotonate of boiling point 88-90" C./12 mm. (prepared by condensing acetaldehyde with methyl acetoacetate in the presence of hydrogen chloride catalyst according to the method of Claisen and Matthews, Ann. 218, 1'72 (1883)) This mixture is thenjheated in the presence of 0.24 part of litharge catalyst \ior 28 minutes at 181-195 C. in apparatus similar to that described in Example 1. During this time, 6 partsof methanol are evolved, indicating nearly complete ester interchange between methyl d- No. 6.5; viscosity F; color 6.0. 'I'hinfilms of this oil containing 0.03% cobalt drier over a steel substrate are hard, light-colored, and tack-free after air-drying for 10-15. hours at' about 25 C. Unmodified linseed oil under the same drying conditions is tacky and eventuallyv dries to a soft, weakfllm. d

' Emmet: 5

Glycerol mired ester of linseed odl acids and a-ace'to-p-(z-jurvl) acrylic acid Per cent a-dcctc-p-(a-iurynacrync acid glyceride 20.0

Linseed acids glyceride 80.0 To 9.8 part of refined glycerol are, added 41' I parts of methyl d-aceto-e-(2-i'uryl) 'acrylate of ,boiling point 156-158 C. rnm. (prepared by condensing iurfural and methyl acetoacetate, using piperidine as catalyst, according to the meth- 0d of Knoevanagel, Ber. 31,-734 (1898)) and 0.32

part 01' litharge. "I'hismixture is heated for 25 minutes at 190-200 C, under the conditions of Example 4. To the partial glyceride thus formed are added 46 parts of linseed oil acids and 183' parts of alkali-refined linseed oil, and the resulting mixture isheated for 12 hours at 200-215- C. under the conditions given in Example 1. The resulting homogeneous oil possesses the following physical and analytical values: N 1.4910; hy-

droxyl No. 18.47; acid No. 7.0-1 viscosityE. Thin P films. of this oil containing 0.03% cobalt over a steel substrate dry to exceptionally hard, flexible, adherent, and tack-'iree films after about 10 hours at room temperature. Such films are strikingly superior to unmodified linseed oil and are also superior in hardness and toughness to films obtained from China-wood oil-limed rosin' var- I nishes or from perilla oil-fAmberoP'varnishes of about 45-gallon oil length.

I ML! 6 Glycerol mixed ester. of linseed oil acids and 2- dceto-5-phenulpentad1e1i-Z,4-oic acid I Per cent 2-Aceto-5-phenylpentadien-2,4-oic acid glyceride Q. 20.0 Linseed acidsglyceride 80.0

"To 5.3 of refined glycerol are added24 parts of methyl 2;aceto-5-phenyltadien-2A-oate of boiling point 183-188 c./2, mm, (prepared by condensing cinnamaldehyde and methyl acetoacetate using pip'eridine catalyst according to the method'oi Knoevanagel, Ber. 31, 734 (1898)) and 0.20 part of litharge catalyst- This mixture is heated for 0.5 hour at 180-200 C. under condipartial glyceride thus formed are added 22..7 parts linseed oil acidsand 95.5 parts ofalkali-refined linseed oil,'and the mixture is heated at ZOO-218 C. for 12 hours under conditions described pre- P aying diglyceride, in the same type of apparatus described in Example 1. A vigorous stream of carbon dioxide is next blown through the reaction mixture at 185 C. for 20 minutes to remove solvent. After being cooled and filtered, the resulting' oil is found to possess the following physical and analytical values:-: hydroxyl No. 11.9; acid No.

4.2; viscosity Z-2. Thin illms of this oil containmg 9.03% cobalt, after drying lor 10-15 hours at room temperature, are very hard, tough, and pos-' sess good flexibility:

The p-dibenzoturoylacrylic above is prepared by stirring asolution of 49 parts .tiops described in previous examples. To the,

or dibenzofurane and 29 parts of m'aleic anhy- .dride in 190 'parts of carbon disulfide with 80' parts of aluminum chlorideior -30 minutes. No external heat is applied since the heat of reaction is sufll'cient to keep the carbon disulilde vi'ously. The resulting homogeneous oil is found to the iollowinfl physical and analytical viscosity E; color 9.0. 'I'hin films oi this oil containing 0.03% cobalt over a steel substrate are hard, light-colored, and tack-tree after air-drying i'or 10-15 hours atabout C. Linseed oil 'under the same drying conditions is tacky and eventually dries to a soft, weal: film having residual tack.

. Exun n 7 Glycerol mixed ester of linseed oil acids and a dCQfO-fl-(Z-fitflllldfiflllifi acid I Y Per cent wa 1.4943; hydroxyl'No. 15.97; acid No.

refluxing. The. crude acid separates when the re-'. action mixture is poured into acidified water. It

is purified by dissolving it in dilute aqueous sodi- -um carbonate, -i'llteri g, and repreclpitating by addition of acid. After washing-in water and drying, the acid melts at 205 C., and has a neutralization equivalent of 269, the calculated value heing 266.

.- hydric alcohol simple ester content within whichs-sceto-p-(z-iuryn acrylic acidglyceride 23.2

Linseed acids 'glyoeride -1... 78.8 To '14- parts 01' linseed 811' diglyceride prepared .as described in Example 1 are added 25 parts of ethyl -aceto-p-(2-iuryl)acrylate and 0.1% 0! litharge based on thelinseed oil diglyceride. This mixture is heated in a carbon dioxide atmosphere with rapid stirring in a vessel fitted with a sepiluxing occurs at the head oi the Iractionating column when the bath temperature is 200-240 C.

Under these conditions, a toluene-ethanol binary boiling at 70-104 C. distills oil. .In this way, the theoretical amount of ethanol (5.5 parts) is 001-! lected during 1.. hours. After rem v a toluene and traces of ethanol from the residue, a hpmogeneous oil the following physical and analytical values is obtained: 1W 1.495; 1137-.

- droxyl No. 64.85; acid No. 24.05. Thin iilms oi this oil containing 0.03% cobalt drier over-a steelsubstrate-ara hard, flexible. adherent, and tack- !rce alter air-drying I Exam le Glycerol mixed ester of linseed oil acids and, p -dibensolurovlocnllgc acid ls-nlb'ensotiu'oylacryiic acidglyceride 32.0

Linseed acids glyceride..

To 61.6 parts oi linseed oil diglyceride described in Example-1- are added 26,6 parts of p-dibensoi'uroylacrylic acid and luparts oi-toluenc. This mixture is refluxed for 4 hours at 175-183 0., cm-

ior 2-3 days at room te1 n' oratory-tunnel, agitator, gas inlet tube, andeiiicient frsctionating column. Enough toluene is introduced into the reaction vessel so that 'repriate selection of proportio For eachparticular combination '0': polyhydric I alcohol, acylacrylic acid, and other monocarboxylic acid, there is a range of 'acylacrylic acid-polythe products dry fastest and have best'film properties generally. .lnregard' to the glycerol mixed esters of acylacrylic acids generally, and more particularly in regard to glycerol mixed esters of B-benzoylacrylic acid anddrying or semi-dryin oil acids (especiallylinsee'd oil acids), it will usually be found that the most valuable products -maximum.possible for the ingredients More specifically, when the polyhydric alcohol is I glycerol,v and the other acid is drying or semidrying' oil acids. it is possible, by appropriate selection of proportions, to prepare a mixed, glycerme having the desired degree of improvement (up Per cent 4 give a mixed ester of the desired scylacrylic acid -ceride content is high (e. g.,abov 26%), the

blending is preferably carried out at elevated to the maximum possible for the ingredients involved) as compared to the drying or semi-dry ing'bil whose acids are being used.

The desired proportion or acylacryllc acid gly-. ceride is normally-obtained by using the calculated amount clan acylacrylic acid or ester-lilable derivatlve. However, an, eflfect which approaches or equals the behavior of the mixed ester so made can be obtained bypreparingamixed estet. of p-acylacrylic glyceride content higher than, that desiredand blending it with'the drying on whose acids are being used (or a diil'erent oil i1- desired) in an amount which is calculated to glyceride content; When the acylacrylic acid sly 0.1% of sodium bisulfate catalyst based on acid reierred to it is possible to, prepare, by appro desired degree oi ix'nmovement in film-forming properties (up to the involvedlf' as compared to the polyhydric alcohol simple es-' ter of theacid other'than' theacylacrylic acid.

2,881,886 a/ mature; suitable conditions are, for example,

the heating of the two oils. with stirring and in an inert gas atmosphere, for about 0.5 hour at about 200 C. Under these conditions, it is probable that some interchange occurs, since the filmforming properties are usually better than those of cold blends of the two oils.

As has been indicated, the simple esters or this invention can be repared by reacting the polyhydric alcohol with the acylacrylic acid, or with an appropriate esterifiable derivative thereof, such as the anhydride, acid halide, or esters of an alcohol more volatile than the polyhydric alcohol whose ester is being prepared. The esteriflcation reaction can be controlled so that one or more of the alcoholic hydroxyls are esterifieri. The reaction temperature can be varied widely. With an acid halide or anhydrlde. temperatures in the neighborhood oi 20-100 C. are sulficient to produce esteriflcation. The direct esteriflcation with acid or the ester interchange process are preferably operated at temperatures above 100 C. and below 275 C.

Also as previously indicated, th mixed esters of the present invention can be made by reacting the polyhydrlc alcohol, simultaneously or successively, in any order, with the several monocarboxylic acids or their esterifiable derivatives. Or a poiyhydrlcalcohol simple ester or either the acylacrylic acid or other acid can be reacted successively with additional poiyhydric alcohol and the remaining acid or acids. In the first. i. e., aicoholysis. step of this latter process, an ester interchange catalyst, such as litharge, sodium hy droxide, sodium alcoholate, etc.,is preferably included in small amount. suitably from 0.01% to 1.0%. The reaction temperature for the alcoholysis can be varied from 150 C. to 300 C., dependmg on the extent of alcoholysis desired, the nature and amount of catalyst present, and the susceptibility of the ester to gelation.

be adjusted to the method chosen, the manner of so doing being apparent to one skilled in the art. when the solution method-heretofore discussed is to be used, any inert water-immiscible liquid which dissolves theproduct is suitable, hydrocar- Solvents and other preparative details should .bons beingpreierable and the amount can be varied as desired. Suitable specific solvents include toluene, nlene, cymene, amy'l benzene,

tetrachloroethane, anisol, and cycloheranone. Aromatic'hydrocarbons, chlorinated solvents, ethcrs. and ketones are suitable in general. A boiling point in the mead-200' c. is desirable. The

processes or the invention can also be carried out in the absence 0! a solvent.

In addition to l ycercl, other polyhydricalcohols can be used in the present invention, such as ethylene glycol, diethylene glycol, triethylene glycol, hexamethylene glycol, tetramethylene glycol, erythrltol, pentraerythritol, sorbitol, manor aliphatic; open or closed chain an 11 the ter, monocyclic, pob y hOmOCYUC. heterocyclic; saturated or unsaturated; straight or branched chain; and substituted or not by other groups or atoms, such as ether, ktI-und, halogen. etc., which do not interfere with the esteriflc'ation reaction.

Any monofunctlonal acyiacrylic acid, as the term i hereinbefore explained, or any esterillable derivative thereof, can be employed. The acyl group can be that 01 any monocarboxylic acid, and it can be present on either the a or {9 carbon. The acid may or may not contain substituent radicals of any kind which do not interfere with the resinirication reaction. Such radicals can be aliphatic or aromatic; open or clcxsed chain, and, if the latter, homocyclic or heterocyclic; saturated or unsaturated; and substituted or not by inert groups, such as ether, ketone, halogen, and sultide. The following speciilc acylacrylic acids can be used in place of the acids of the examples with similar results:

5- (Z-naphthoyl) acrylic acid.

pi i-methoxybenzoyl) acrylic acid, p-(Benzoyl) -u,p-dimethylacrylic acid, p-Acetylacrylic acid... 4-ketoheptadien-2,5-oic acid, a-Acetosorbic acid,

a-ACCtOflQlYhG acid. u-Benzoylcrotonic acid, and e-Furoylcinnamic acid.

In addition-to the particular coating compositions of the examples, the present esters can be formulated into any other desired type of paint. varnish, lacquer, or enamel. Thus, they can be blended by conventional method with other varnish gums, such as copal, kauri, ester gum, oilsoluble. phenol-formaldehyde resins, and rosinextended p yde resins, such as "Ambercls; with other resins, such a vinyl or urea-formaldehyde typ s; with cellulosederivatives, such as nitrocellulose, cellulose acetate cellulose aceto-pr pi nd ethyl cellulose; with auxiliary components of all kinds, such as waxes, solvents; pigments, and pla ticizers as needed and desired; and to particular advantage with fatty oils, especially drying or semi-drying oils, as is explained above.

These compositions can be applied to many kinds of surfaces and materlals, for example, wood, metal, paper, linen, silk, cotton, other textiles. and regenerated cellulose wrapping foils. Specific manufactures that can be so produced are linoleum, patent leather, llnoxyn-type materials, coated copper wire, oiled cloth, oiled silk, printing inks, and sandpaper. The products of the in vention can also be .made up into molding compositions, putties, and the like. In addition, they can be employed as modliyi il agents for ureaiormaldehyde and phenol-formaldehyde resins.

It will be apparent from the foregoing description that new esters having remarkable properties and a wide utility have been obtained, In particular, these esters are valuable substitutes for the natural drying oils in coating compositions, thereby reducing materially the dependence upon these natural products. The new esters have also many advantageous properties not shared by the natura1 oils. as, for example, the remarkable ability to 'form films which do not crystallize, wrinkle, 0r

frost, a do films from the more rapidly drying natural oils, such as China-wood oil. Furthermore, it is possible to take any fatty oil, including one that has a low order of drying, and, by substltutlng a part of the fatty acid making up that oil by an acylecrylic acid. to lmm'ove the dryini and dim properties neatly. The com ositions of the present invention are particularly outstanding in that they combine the hixhillm build oi the natural drying oils (resultinz from the much higher solids content at workin: visoositiee) with the ability or resin-oil varnishes to-dry rapidly to hard.- touzh films.

It is apparent that many widely diflerent embo'diments of this invention may be made withoutdepartina irom the spirit and scope thereof; and, therefore. it is not intended to be limited except as-indicated In the'a'ppended claims. v

l2 claim:

2. A glycerol ester of an acylacrylic acid.

3. A polyhydrie alcohol mixed ester of an acylscrylic acid and another monoiunctional monooarboxylic acid. v

4. A glycerol mixed eater of an aeylacrylic acid and mother monoiunctional monocarboxylic acid.

5. A'giyeerol mixed ester 0! an acylacrylic acid and the ecids of a natural iatty oil.

6. A glycerol mixed ester 01 an acylwrylic acid and the acids of a natural drying oil.

7. A polyhydric alcoh'oi mixed ester the acidic radicals or which comprise those of anaoylacrylic acid and o! a monoi'unctional monocarboxylio 1. it"poly aloohol este ot-an aoylacrylicin acid or different atructure. .aoid. by r MARTIN E. CUP'ERY.

Patent no; 2,581,886.

August 11+, 1915.

. MARTIN E. CUPERI- It is hereby eertii iod that error eppoars in the irritated specification or the above numbered patent requiring correctionasffollhue: Page 11., first column, line 11, for 5-1pheny1tadien" read --5-pheny1entadien,-- and that the said Letters Patent should be read with this correction thereinthat the I same w conform 5.515 record oi the ease in the Patent Office. I

Signed and sealed this 13th on or December, A. n. 191

Lealielrezer First Assistant Oanni-ssioner or Patents.

oil by an acylecrylic acid. to lmm'ove the dryini and dim properties neatly. The com ositions of the present invention are particularly outstanding in that they combine the hixhillm build oi the natural drying oils (resultinz from the much higher solids content at workin: visoositiee) with the ability or resin-oil varnishes to-dry rapidly to hard.- touzh films.

It is apparent that many widely diflerent embo'diments of this invention may be made withoutdepartina irom the spirit and scope thereof; and, therefore. it is not intended to be limited except as-indicated In the'a'ppended claims. v

l2 claim:

2. A glycerol ester of an acylacrylic acid.

3. A polyhydrie alcohol mixed ester of an acylscrylic acid and another monoiunctional monooarboxylic acid. v

4. A glycerol mixed eater of an aeylacrylic acid and mother monoiunctional monocarboxylic acid.

5. A'giyeerol mixed ester 0! an acylacrylic acid and the ecids of a natural iatty oil.

6. A glycerol mixed ester 01 an acylwrylic acid and the acids of a natural drying oil.

7. A polyhydric alcoh'oi mixed ester the acidic radicals or which comprise those of anaoylacrylic acid and o! a monoi'unctional monocarboxylio 1. it"poly aloohol este ot-an aoylacrylicin acid or different atructure. .aoid. by r MARTIN E. CUP'ERY.

Patent no; 2,581,886.

August 11+, 1915.

. MARTIN E. CUPERI- It is hereby eertii iod that error eppoars in the irritated specification or the above numbered patent requiring correctionasffollhue: Page 11., first column, line 11, for 5-1pheny1tadien" read --5-pheny1entadien,-- and that the said Letters Patent should be read with this correction thereinthat the I same w conform 5.515 record oi the ease in the Patent Office. I

Signed and sealed this 13th on or December, A. n. 191

Lealielrezer First Assistant Oanni-ssioner or Patents. 

